Cyclic Voltammograms Research Articles

Efficient electrochemical determination of Sudan I in food samples based on modified electrode by using Ni-Fe layered double hydroxide nanosheets and ionic liquid

Sudan I, is one of the commonly used azo dyes in food samples, which has shown adverse effects on human health. Therefore, determining the level of Sudan I in food samples can be very effective in ensuring food safety and protecting human health. In this study, an electrochemical sensing platform was designed using Ni-Fe layered double hydroxide nanosheets and ionic liquid modified carbon paste electrode (Ni-Fe LDH/ILCPE) which was utilized to determine Sudan I. Comparison of cyclic voltammograms of Sudan I on the unmodified CPE and Ni-Fe LDH/ILCPE showed that, the higher oxidation currents were obtained on the surface of the Ni-Fe LDH/ILCPE, indicating that the modified CPE owns significant surface improvement effects and good electrochemical performance in detecting Sudan I. Under optimized conditions, the developed Ni-Fe LDH/ILCPE sensor demonstrated a linear relationship between the voltammetric response and Sudan I concentrations from 0.03 µM to 510.0 µM with a low detection limit (LOD) of 0.01 µM based on S/N = 3.0. Additionally, the Ni-Fe LDH/ILCPE platform exhibits high accuracy, with a recovery of 96.4 % to 104.1 % for Sudan I determination in food samples including Ketchup and Chilli powder, which implies that it will be a potential detection method for Sudan I detection.

Cold and Liquid Crystal Properties of Square-Planar Copper(II) Versus Nickel(II)- Iminophenolate/Naphthalen-2-Olate Schiff Base Complexes.

Reaction of the phenolate or naphthalen-2-olate based Schiff base ligands, (E)-1-((2-ethylphenylimino)methyl)phenol (HL1) or (E)-1-((2-ethylphenylimino)methyl)naphthalen-2-ol (HL2) with nickel(II) and copper(II) acetate provides the complexes bis[(E)-1-((2-ethylphenylimino)methyl)phenolato-ĸ2N,O]Ni/Cu(II), [Ni(L1)2] (1) and [Cu(L1)2] (2), or bis[(E)-1-((2-ethylphenylimino)methyl)naphthalen-2-olato-ĸ2N,O]Ni/Cu(II), [Ni(L2)2] (3) and [Cu(L2)2] (4), respectively. Single crystal X-ray structure determinations for 1, 3 and 4 reveal N2,O2-metal coordination of two chelating Schiff base ligands in a square-planar geometry. Powder X-ray diffractograms confirm the phase purity of the bulk microcrystalline samples. Thermal analyses by differential scanning calorimetry (DSC) and polarized light microscopic (PLM) indicate the copper(II) complexes to exhibit cold crystal (2) and liquid crystal (4) property. Cyclic voltammograms suggest an irreversible electrochemical process with two one electron charge transfer processes in N,N-dimethylformamide. Variable temperature magnetic measurements at the solid-state prove the diamagnetic nature of the low-spin Ni2+ centres in 1 or 3, as expected from the square-planar coordination geometry with rather strong ligands. The complexes expose medium level of antioxidant activity in methanol. Optimized geometry and excited state property by DFT/TD-DFT correspond well to the experimental results of the electronic and molecular structure at the ground state.

Electrochemical Drawdown of U3+ and Ce3+ in Molten LiCl-KCl Using a Liquid Cadmium Cathode

Abstract The electrorefining of spent nuclear fuels is a key step to recover uranium and transuranium on separated cathodes. However, the electrolyte salts become contaminated with fission products after batches of electrorefining, and therefore the two unit processes for the drawdown of actinide and lanthanide are suggested before treatment of the contaminated salts. We investigated the electrochemical drawdown of U3+, Ce3+, and U3+ from Ce3+ in molten LiCl-KCl electrolyte using a liquid cadmium cathode (LCC) at 773 K. The drawdown mechanism of U3+ and Ce3+ was determined by cyclic voltammograms and calculating the equilibrium potential. After galvanostatic electrolysis, high recovery yields were obtained for the drawdown of U3+ and Ce3+, but the current efficiency of Ce3+ was at least twice as high as that of U3+ due to the cyclic electrolysis of U3+/U4+. Despite significant underpotential deposition of Ce3+ in the LCC, an exceptional separation factor for Ce relative to U reached 84.67 ± 17.13, which was attributed to the formed pure uranium products hindering the subsequent deposition of Ce3+. Moreover, pure uranium products and Ce-Cd intermetallic compounds were characterized by X-ray diffraction and scanning electron microscope coupled with energy dispersive X-ray spectroscopy.

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal-Ligand Cooperativity.

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [CoIIICp(PPh2NBn2)(CH3CN)]2+ to [HCoIIICp(PPh2NBn2)]+. This complex catalytically converts CO2 to formate under CO2 reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the PPh2NBn2 ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation. We reveal three unique PCET mechanisms, and we show that the amine on the PPh2NBn2 ligand serves as a kinetically accessible protonation site en route to the thermodynamically favored cobalt hydride. Cyclic voltammograms recorded with proton sources that span a wide range of pKa values show four distinct regimes where the mechanism changes as a function of acid strength, acid concentration, and timescale between electrochemical steps. Peak shift analysis was used to determine proton transfer rate constants where applicable. This work highlights the astute choices that must be made when designing catalytic systems, including the basicity and kinetic accessibility of protonation sites, acid strength, acid concentration, and timescale between electron transfer steps, to maximize catalyst stability and efficiency.

Modification Of a Screen-Printed Carbon Electrode with Nanoporous Gold by Electrodeposition and Dealloying of a Gold-Copper Alloy

In this study, a three-dimensional structure of nanoporous gold (NPG) was made by selectively corroding copper (Cu) from gold-copper (Au-Cu) alloys using a two-step electrochemical method. Given its large surface area and interconnected porous network, nanoporous gold is a suitable material for the advancement of electrochemical sensors. The screen-printed carbon electrode (SPCE) modified with nanoporous gold (NPG/SPCE) was fabricated by electrodepositing a gold-copper alloy from gold ion (Au3+) and copper ion (Cu2+) solution via cyclic voltammetry (CV) by scanning from -0.3 V to -0.8 V for 80 cycles. The copper is then removed via a dealloying process in 3M HNO3 using the cyclic voltammogram (CV) method by scanning potential from 0 V to +1.0 V for 100 cycles at 100 mV/s. The morphology, elemental composition, and electrochemical active surface area (ECSA) of NPG/SPCE electrodes were characterized using FESEM, EDX, and CV analysis, respectively. The electrochemical performance of the NPG/SPCE was compared with bare SPCE in a 10 mM potassium ferrocyanide (K4FeCN6) solution using cyclic voltammetry. The morphological study using FESEM revealed that the NPG/SPCE had an average pore diameter of 53 nm. The quantification of elements using EDX shows that 84 % of the copper in the electrodeposited gold-copper alloy electrode was successfully removed by the dealloying process. The higher number of cycles during the dealloying process led to producing NPG with higher ECSA electrodes. The ECSA of NPG/SPCE is 12 times greater than that of bare or unmodified SPCE in an equivalent geometrical area. NPG/SPCE has a much better electron transfer surface than bare SPCE due to its high surface area and gold surface properties, making it a potential sensing material for biosensing applications.

The Influence of Thermal Treatment of Activated Carbon on Its Electrochemical, Corrosion, and Adsorption Characteristics

Activated carbons can be applied in various areas of our daily life depending on their properties. This study was conducted to investigate the effect of thermal treatment of activated carbon on its properties, considering its future use. The characteristics of activated carbon heat-treated at temperatures of 1500, 1800, and 2100 °C based on its future use are presented. The significant effect of the treatment temperature on morphological, adsorption, electrochemical, and corrosion properties was proved. Increasing the temperature above 1800 °C resulted in a significant decrease in the specific surface area (from 969 to 8 m2·g−1) and material porosity—the formation of mesopores (20–100 nm diameter) was observed. Simultaneously, adsorption capability, double layer capacity, and electrochemically active surface area also decreased, which helped to explain the shape of cyclic voltammograms recorded in 2,4-dichlorophenoxyacetic acid and in supporting electrolytes. However, a significant increase in corrosion resistance was found for the carbon material treated at a temperature of 2100 °C (corrosion current decreased by 23 times). Comparison of morphological, adsorption, corrosion, and electrochemical characteristics of the tested activated carbon, its applicability as an electrode material in electrical energy storage devices, and materials for adsorptive removal of organic compounds from wastewater or as a sensor in electrochemical determination of organic compounds was discussed.

Improving the Performance of the Layered Nickel Manganese Oxide Cathode of Sodium-Ion Batteries by Direct Coating with Sodium Niobium Oxide.

This research highlights the efficacy of NaNbO3 as a coating for P2-Na2/3Ni1/3Mn2/3O2 cathodes in sodium-ion batteries. The coating enhances the kinetic behavior and cyclability of the electrochemical cells, as shown by electrochemical measurements. XRD analysis indicates that Nb does not incorporate into the cathode structure, implying a physical interaction between the coating and the cathode material. XRF analysis and EDX mapping confirm the actual composition and uniform dispersion of elements throughout the sample, while the electron micrographs evidence the occurrence of NaNbO3 particles modifying the surface of the layered oxide. The Ni4+/Ni3+ and Ni3+/Ni2+ redox pairs, along with the partially reversible oxidation of oxide to peroxide anions, contribute significantly to cell capacity, as revealed by XPS spectra. This last effect and the appearance of a co-intercalated phase at high voltage are positive factors to provide fast kinetics. Cyclic voltammograms show that samples coated with 2-3% NaNbO3 have superior rate capability, with high capacitive response and apparent diffusion coefficients. These samples also have low impedance at the electrode-electrolyte interface, which helps deliver a high capacity at 5C. Further cycling at 1C shows improved cyclability in the bare and 3% coated samples, due to their higher diffusion coefficients on charging. Notably, the 3% NaNbO3-coated sample exhibits excellent cyclability below 0 °C, making it a promising cathode material for sodium-ion batteries.

Mechanistic Insights into the Potentiodynamic Electrosynthesis of PEDOT Thin Films at a Polarizable Liquid|Liquid Interface.

Conducting polymer (CP) thin films find widespread use, for example in bioelectronic, energy harvesting and storage, and drug delivery technology. Electrosynthesis at a polarizable liquid|liquid interface using an aqueous oxidant and organic soluble monomer provides a route to free-standing and scalable CP thin films, such as poly(3,4-ethylenedioxythiophene) (PEDOT), in a single step at ambient conditions. Here, using the potentiodynamic technique of cyclic voltammetry, interfacial electrosynthesis involving ion exchange, electron transfer, and proton adsorption charge transfer processes is shown to be mechanistically distinct from CP electropolymerization at a solid electrode|electrolyte interface. During interfacial electrosynthesis, the applied interfacial Galvani potential difference controls the interfacial concentration of the oxidant, but not the CP redox state. Nevertheless, typical CP electropolymerization electrochemical behaviors, such as steady charge accumulation with each successive cycle and the appearance of a nucleation loop, were observed. By combining (spectro)electrochemical measurements and theoretical models, this work identifies the underlying mechanistic origin of each feature on the cyclic voltammograms (CVs) due to charge accumulated from Faradaic and capacitive processes as the PEDOT thin film grows. To prevent overoxidation during interfacial electrosynthesis with a powerful cerium aqueous oxidant, scan rates in excess 25 mV·s-1 were optimal. The experimental methodology and theoretical models outlined in this article provide a broadly generic framework to understand evolving CVs during interfacial electrosynthesis using any suitable oxidant/monomer combination.

Lanthanide detection by novel arylether based receptor with imine functional groups: synthetic, photophysical, electrochemical and computational elucidation

AbstractThe present research discloses a novel chemical sensor (TEI) [1-((E)-(2-(3-(2-((E)-(2-hydroxynaphthalene-1-yl)methyleneamino)phenoxy)phenoxy)phenylimino)methyl)naphthalene-2-ol] for the detection of rare earth element cerium (III) in which spectrophotometric and voltametric sensor techniques were used with a versatile combination of ether and imine group. Various lanthanide ions were checked for the binding in a solution of TEI under identical conditions, including Ce(III), Dy(III), Ho(III), La(III), Sm(III), Eu(III), Gd(III), Tb(III), Er(III), Yb(III), Tm(III), Pr(III) and Nd(III). As observed in absorption studies, the enhancement of spectral intensity at 310 nm caused by Ce(III) was expected over other lanthanide ions. Cyclic and differential pulse voltammograms were also drawn for TEI receptor with and without Ce3+ ions With incremental addition of Ce3+ ions the anodic peak at 0.68 V oxygen gets completely diminished. Another anodic peak at 0.75 V which was due to complete oxidation of ether group and re-oxidation of reduced imine group, got reduced. In case of cathodic peak (due to reduction of imine group) at 0.6 V, there was hardly any decrease in current. This leads to the confirmation that there was no involvement of imine group in binding in the complex. Detection limit obtained by this sensor is 5 × 10–7 M without any interference which makes it a potent sensor for cerium detection.

Nanoclay composites in electrochemical sensors

Nanoclays are layered structures in the nanoscale range with widespread application due to their unique properties such as swelling, cation exchange capacity, and ease of functionalisation using metals, metal oxides, and organic compounds such as carbon paste, polymers, and other biomolecules that form nanoclay composites. Nanoclay functionalisation with silver (Ag), zinc oxide (ZnO), and bimetallic silver–gold (Ag–Au) using hydrophilic and hydrophobic clays is here evaluated and discussed. The composites’ synthesis and morphological, crystallinity, and electroactive properties in comparison with pure nanoclay are also assessed. The layered structure and crystallinity of all these nanoclay composites were slightly changed. The clumped layered structures on the surface of the nanocomposites had dispersed white spots that indicated possible surface modification. The nano-films of the composites’ electroactivity were comparatively high, as seen from the increase in current in the cyclic voltammetry characterisation voltammograms and the differential pulse voltammograms of the pharmaceutical detection. Efavirenz, nevirapine, and zidovudine detection was improved by modification of the nanocomposite with human serum albumin (HSA), as shown by the higher current, thus indicating improved conductivity of the composites compared to the pure nanoclays. Applying HAS-modified nanocomposites in the analysis of efavirenz, nevirapine, and zidovudine on a glassy carbon electrode (GCE) showed good linearity and acceptable detection limits comparable to those of previous studies. Therefore, it has potential for application in pharmaceutical quality control and environmental monitoring.

Redox-Detecting Deep Learning for Mechanism Discernment in Cyclic Voltammograms of Multiple Redox Events

Redox-Detecting Deep Learning for Mechanism Discernment in Cyclic Voltammograms of Multiple Redox Events

Microbial Fuel Cell Based on Ensifer meliloti

The world’s growing energy crisis demands renewable energy sources. This issue can be solved using microbial fuel cells (MFCs). MFCs are biocatalytic systems which convert chemical energy into electrical energy, thereby reducing pollution from hazardous chemical compounds. However, during the development of MFCs, one of the most significant challenges is finding and assessment of microorganisms that generate sufficient redox potential through metabolic and catalytic processes. In this research, we have used Ensifer meliloti (E. meliloti) bacteria to design MFCs based on consecutive action of two redox mediators (9,10 - phenanthrenequinone (PQ) and potassium ferricyanide), which transferred charge between E. meliloti bacteria and graphite rod electrode. A viability study of E. meliloti culture showed that PQ significantly inhibits the growth of bacteria at 0.036 mM. Cyclic voltammograms were registered in the presence of 20 mM of potassium ferricyanide and different concentrations (0.036 and 0.071 mM, 0.11 mM, 0.14 mM, 0.172 mM, 0.32 mM) of PQ. Four days of lasting assessment of the microbial fuel cells in two-electrode systems showed that the maximal open circuit potential during the experiment raised from 174.9 to 234.6 mV. Power increased from 0.392 to 0.741 mW m−2.

Evaluation of electrodeposition synthesis of gold nanodendrite on screen-printed carbon electrode for nonenzymatic ascorbic acid sensor

Gold nanodendrite (AuND) is a type of gold nanoparticles with dendritic or branching structures that offers advantages such as large surface area and high conductivity to improve electrocatalytic performance of electrochemical sensors. AuND structures can be synthesized using electrodeposition method utilizing cysteine as growth directing agent. This method can simultaneously synthesize and integrate the gold nanostructures on the surface of the electrode. We conducted a comprehensive study on the synthesis of AuND on screen-printed carbon electrode (SPCE)-based working electrode, focusing on the optimization of electrodeposition parameters, such as applied potential, precursor solution concentration, and deposition time. The measured surface oxide reduction peak current and electrochemical surface area from cyclic voltammogram were used as the optimization indicators. We confirmed the growth of dendritic gold nanostructures across the carbon electrode surface based on FESEM, EDS, and XRD characterizations. We applied the SPCE/AuND electrode as a nonenzymatic sensor on ascorbic acid (AA) and obtained detection limit of 16.8 μM, quantification limit of 51.0 μM, sensitivity of 0.0629 μA μM−1, and linear range of 180–2700 μM (R2 value = 0.9909). Selectivity test of this electrode against several interferences, such as uric acid, dopamine, glucose, and urea, also shows good response in AA detection.

Sensitive Electrochemical Sensing Properties for Cyanide Detection Using Polyaniline/Cu-Vanadate Nanobelt-modified Electrode

Background: Cyanide is a toxic anion and may be discarded into the water environment, which is a serious threat to human beings and the environment. Hence, it is essential to explore a facile, sensitive method for cyanide detection. Polyaniline/Cu vanadate nanobelts serve as electrode materials for sensitive cyanide determination. Methods: Polyaniline/Cu vanadate nanobelts were obtained by a simple route using polyaniline, Cu vanadate nanobelts. The polyaniline/Cu vanadate nanobelts were measured via electron microscopy, diffraction, infrared spectrum, and electrochemical methods. Results: Amorphous polyaniline nanoparticles with a particle size of about 100 nm were attached firmly to the surface of Cu vanadate nanobelts. Electrochemical sensing properties for cyanide detection were analyzed using a cyclic voltammetry technique using the nanobelts-modified electrode. The cyclic voltammograms (CV) peaks centered at +0.64 V and +0.54 V were observed using the polyaniline/Cu vanadate nanobelts in 0.1 M KCl solution with 2 mM cyanide. The proposed composite nanobelt-modified electrode possessed the detection range and detection limit of 0.001-2 mM and 0.22 μM, respectively. Conclusion: Polyaniline greatly enhances the electro-catalytic performance of the Cu vanadate nanobelt-modified electrode for cyanide detection.

Evaluation of the Solid-Electrolyte Interphase Formation in a Bis(fluorosulfonyl)amide Based Ionic Liquid in the Presence Lithium Ion Using Different Redox Probes

The SEI formation in 0.5 M LiFSA/BMPFSA was investigated using different redox probes. The redox reaction of a metallocene and organic compound on a Pt electrode were investigated by cyclic voltammetry in BMPFSA and 0.5 M LiFSA/BMPFSA. Cyclic voltammograms were taken after holding the electrode at different potentials for 1 h. The cyclic voltammograms were unchanged in BMPFSA, indicating that BMPFSA was stable in the measured potential range and that the redox reaction was not affected by a change in the electric double layer structure. On the other hand, peak shifts were observed in the presence of Li+ at potentials more negative than –1.1 V vs. Ag|Ag(I), attributed to a decrease in the electron transfer rates and indicating that the SEI formation promoted by the interaction between Li+ and FSA– affects the redox reactions not only of metallocene but also of organic compounds that undergo outer sphere electron transfer reactions.

Synthesis and performance of PdAu/ITO electrocatalysts in urea oxidation reaction

PdAu electrocatalysts were prepared in different atomic compositions supported on ITO by sodium Borohydride process. XRD results show intense crystalline peaks related to ITO, which may mask the appearance of less crystalline Pd or Au phases. Transmission results indicate agglomeration of palladium and gold nanoparticles on the support, a phenomenon compatible with metal oxide supports. Cyclic voltammograms in the absence of urea display characteristics commonly observed for PdAu electrodes, with an increase in oxygenated species compared to pure Pd or Au. Voltammograms in the presence of urea showed oxidation processes and lower current values, indicating catalyst deactivation processes. PdAu 75:25 demonstrated higher power density values compared to other prepared electrocatalysts, suggesting a synergy between Pd and Au for urea oxidation reaction.

Phosphorus-Nitrogen Compounds: Part 76. Design and Syntheses of Dispiro- and Trispiro(N/N)cyclotriphosphazenes: Conformational and Structural Analyses, Chirality, Electrochemical, Dye-Sensitized Solar Cells, and Bioactivity Studies.

The reactions of monospirocyclotriphosphazenes (1 and 2) with N-methyl-1,3-diaminopropane gave unsymmetrical cis-(3 and 5) and trans-(4 and 6) dispirocyclotriphosphazenes. Trans-cis-trans (tct) (7 and 11), cis-cis-cis (ccc) (8 and 12), trans-trans-cis (ttc) (9 and 13), and cis-trans-trans (ctt) (14) trispirocyclotriphosphazenes were obtained from the reactions of 3 and 5 and 4 and 6 with N-methyl-1,3-diaminopropane. cis-Dispirocyclotriphosphazenes (3 and 5) exist as "pseudomesoracemates", while trans-dispirocyclotriphosphazenes (4 and 6) are in "racemates". The existences of cis-3 and trans-4 as "pseudomesoracemate" and "racemate" were confirmed by 31P NMR spectra recorded by the addition of "chiral solvating agent (CSA)". X-ray crystallography proved that the absolute configurations of each enantiomer of cis-5 and trans-6 are SS' and RS'. Trispirocyclotriphosphazenes tct, ttc, ccc, and ctt exist as racemates, pseudomesoracemate, and meso forms. Furthermore, Hirshfeld surface analysis of the crystal structures of cis-5 and trans-6 revealed that the most significant contribution to crystal packing comes from H···H (58.2 and 57.6%, respectively). An oxidation-reduction wave was detected in the reversible cyclic voltammograms of the phosphazenes. The highest power conversion efficiency in dye-sensitized solar cell studies was obtained with cis-5. Additionally, trans-6 exhibited the lowest minimal inhibitory concentration value (78.1 μM) against Candida tropicalis, and it was observed to cleave pBR322 plasmid DNA.

A study of electrochemiluminescence mechanism of Rubrene/TPrA system in an aqueous solution via stochastic collision electrochemistry in an emulsion reactor

BackgroundElectrochemiluminescence (ECL) is an electrochemically induced process in which radicals generated at the electrode surface undergo exergonic electron transfer reaction to form excited states and luminesce. ECL, with high sensitivity and superior spatiotemporal control, has been widely applied in bioanalysis and light-emitting devices. The ECL signal of rubrene (Rub) was observed in Rub/TPrA oil-in-water (o/w) emulsions, which was inconsistent with the theory of ion-transfer coupled electron-transfer in Rub emulsion droplets, and the conventional ECL mechanism in Rub/TPrA system couldn't explain this phenomenon. ResultsChoosing the toluene oil-in-water emulsion droplets as reactors, we put forward and verified a new ECL mechanism of Rub in aqueous solution on the basis of cyclic voltammograms, single-entity electrochemistry, ECL detection techniques and COMSOL finite element simulation. The new mechanism involved that Rub was reduced to Rub•- by the highly reducing species TPrA•, Rub•- was then oxidized to the excited state Rub∗ by the stable intermediate TPrA•+, and finally Rub∗ was inactivated by emitting photons. In simulation, the standard oxidation rate constant of TPrA in the emulsion droplets was deduced as 1.5 × 10−4 cm/s, and the deprotonation rate of TPrA•+ was about 200 s−1. Besides, emulsion droplets colliding on Au ultramicroelectrode (UME) were found to be able to amplify ECL signals. SignificanceThe newly proposed ECL mechanism of Rub/TPrA emulsion reactors broke the solubility problem of Rub in an aqueous, promoting the research and application of the organic luminophore Rub in bioanalysis. With the ECL signals amplification capability, the o/w emulsion reactors are promising to future design of ECL biosensors with higher sensitivity.

Facile synthesis of spherical-shaped CeC2–TiO2 nanocomposite electrocatalyst with boosted alkaline OER

Developing noble metal-free multifunctional electrocatalysts to catalyze water oxidation is vital for future renewable energy systems. Herein, through several defect modifications, the CeC2–TiO2 nanocomposite on the strength of enriched oxygen vacancies was successfully fabricated by facile hydrothermal method on SS (stainless steel) substrate, attributed to the conductive ability for fast electron transportation. A well-defined phase growth, vibrational bonding of metal atoms, morphological determination, and elemental composition for synthesized heterostructured electrocatalysts were revealed by XRD, FTIR, TEM, and EDX, respectively. XPS has complied to understand the moderate binding energies of CeC2–TiO2 for OER intermediates, which signifies the strong interactions between electronic states of Ce, C, Ti, and O atoms. With the plentiful catalytic active sites, the resultant CeC2–TiO2 entails low overpotentials of only 169 mV and 108.8 mV/dec Tafel slope to afford 10 mA cm−2 for OER in 1.0 M KOH are tested through cyclic and linear sweep voltammogram measurements, thereby exhibit promising activity in alkaline water electrolysis. EIS measurements revealed a decreased polarization resistance for the composite dominated by the small semicircle diameter, corresponding to the adsorption of intermediates. Finally, observed results strongly recommended that the CeC2–TiO2 catalyst exhibited superior OER performance due to excellent electrical chemical coupling between CeC2 and TiO2.

Spectroelectrochemical study of carbon structural and functionality characteristics on vanadium redox reactions for flow batteries.

Vanadium redox flow batteries have applications for large-scale electricity storage. This paper reports the influence of carbon structural characteristics of sustainable walnut shell-derived carbons in carbon/polyvinylidene fluoride composite electrodes on vanadium redox reactions. Pyrolysis, gasification, and chemical treatment procedures were used to modify the structural characteristics of carbons. Carbon functional groups were modified by chemical treatment with HNO3, heat treatment with K2CO3, and high-temperature NH3 treatment. Carbon porous structures were characterized using gas adsorption studies. Raman spectroscopy and X-ray diffraction were used to characterize the carbon molecular structure. Functional groups were characterized using X-ray photoelectron spectroscopy, acid/base titrations, temperature-programmed desorption, and Fourier transform infrared spectroscopy. The influence of carbon structure, porosity, and surface functional groups on the redox reactions of vanadium was investigated using cyclic voltammetry and electrical impedance spectroscopy. The VO2+/VO2 + and V2+/V3+ couples had well-defined peaks in cyclic voltammetry, with the former being the most intense, but the V3+/VO2+ couple was not observed for samples carbonized under nitrogen. The results show that V2+/V3+ and VO2+/VO2 + couples observed in cyclic voltammograms were enhanced for carbonization temperatures up to 800 °C. Electrical impedance spectroscopy also showed impedance trends. The electrochemistry results are primarily related to changes in carbon structure and the catalysis of V3+ oxidation by surface functional groups in the carbon structure. The V3+/VO2+ couple was limited by slow kinetics, but it occurs on specific oxygen and nitrogen sites in the carbon structure. The oxidation of V(iii) to V(iv) only occurs on a limited number of surface sites, and the outer-sphere electron transfer to oxidize V(iii) takes place at much more positive potentials. The coulombic, voltage, and energy efficiency of the carbon electrodes were suitable for batteries.